1302915 九、發明說明： 【發明所屬之技術領域】 本發明係關於塗層組合物。 【先前技術】 經常希望提供-種具有良好光學特性之塗層、薄膜或薄 膜層。舉例而言，某些所要之光學特性為透明度、無霧度 及無色度。一特別希望之光學特性為相對低色階之黃度= 且經常希望在該塗層老化過程中保持相對低色階之黃度。 有時由於要將塗層施用於一基板，且希望塗層之存在$可 能不改變該基板之外觀，因此希望其有良好之光學特性。 有％夕層塗層與基板相互堆疊（例如當將經塗覆之基板繞 成卷時）’且希望由此形成之堆疊具有良好之光學特性。二 us 2002/GG82319揭示以基於納之乳化劑、引發劑、緩衝 2中和劑製備之2,段乳液聚合物，其組成中亦含有低 含量之伸乙基二胺四乙酸（EDTA)。 發明者所面臨之問題為提供乾燥時可用作塗層之含水聚 口物組合物具有比先前已知之組合物更低之黃度，且老化 時保持其低色Pk黃度。吾人已發現此問題可藉由提供含 水之聚合物組合物得以解決，該等組合物將全部或幾乎全 部氛化合物自該組合物中排除且在該組合物中包含足夠量 之至少一種配位劑。 【發明内容】 ,在本發明之第-態樣中’提供一種製備乾燥時適合用作 塗層之含水組合物之方法，其包括： 93198.doc 1302915 U)提供至少一種含水聚八 ^ ^ ^ ^ 〇物，其係藉由至少一種乙烯系 不飽和早體之聚合作用來 试姑a 衣備，且具有-8(TC至ll〇t之玻 璃轉變溫度，及 (b)添加基於該至少一 禮λκ合物之乾重以重量計至少 1〇 ppm之至少一種配位劑， ，、中β έ水組合物含有基於該至 >、-種聚合物之乾重以重量計〇至1〇〇啊的氨化合物。 ,、在本發明之第二態樣中，提供一種製備乾燥時適合用作 塗層之含水組合物之方法，其包括： (a)提供至少一種含水聚合物 飽和單體之聚合作用製備 變溫度，及 ’其係藉由至少一種乙烯系不 且具有-80°C至110°C之玻璃轉 (b)添加基於該至少一種聚合物之乾重以重量計至少卯㈤ 之至少一種配位劑，其中在該含水組合物之該製備中所 使用之成份不包含氨化合物。 在本發明之第三態樣中，提供一種乾燥時適合用作塗層 之含水組合物，其包括： (a)至少一種含水聚合物，其藉由至少一種乙烯系不飽和單 體之聚合作用製備且具有-80°c至11〇°c之玻璃轉變溫 度， (b)基於該至少一種聚合物之乾重以重量計至少10 ppm至 少一種配位劑，及 (C)基於該至少_種聚合物之乾重以重量計〇至1〇〇 ρριη氨 化合物。 【實施方式】 93198.doc 1302915 本文所用之塗層為施用於一基板之一或多層材料。該塗 層可具有幾種目的中之任一種，其包括（例如）保護基板、裝 飾基板、將兩個或兩個以上基板黏附在一起、密封基板、 填充基板中之裂縫、其它用途或其組合。塗層可為連續或 不連續層；塗層可相對較薄或可相對較厚。 本發明之實施涉及使用載運於含水介質中之含水聚合 物。’’載運於’’在本文中意謂溶解於、分散於、懸浮於、亦 及承載於、或其任意組合。該含水介質通常為基於該介質 之重量至少50重量％水、或至少75重量％水、或至少90重量 %水。在某些實施例中，藉由溶液聚合、懸浮液聚合、乳 液聚合、或其組合於水介質中製備含水聚合物。在某些實 施例中，該含水聚合物在含水介質外產生（例如藉由非水溶 劑中之溶液聚合或藉由本體聚合）且接著與含水介質組合 形成含水聚合物。 在某些實施例中，藉由此項技術中已為吾人所知之含水 乳液聚合（如 M.S. El-Aasser 及 E.D. Sudol 在由 P.A. Lovell 及 M.S. El-Aasser 主編、由 John Wiley and Sons 1997 年出版之 Emulsion Polymerization and Emulsion Polymers第二章中 所述）製備該含水聚合物。含水乳液聚合涉及在一反應器中 於水介質中形成單體小液滴乳液（意即”乳化”該單體），其通 常藉由至少一種界面活性劑之存在來穩定。含水乳液聚合 中所使用之單體為能參與自由基聚合之化合物。單體小液 滴可含有單一單體或單體混合物。 在多數含水乳液聚合過程中使用一或多種引發劑。引發 93198.doc 1302915 ^為吾人認為響應例如升高之溫度、化學反應或輻射(如光 2、電子、γ射線、或其組合）之某些刺激產生自由基之化 一物某些《用引發劑為過硫酸鹽。其它常用引發劑為有 4及…、機過氧化物。吾人認為引發劑產生之自由基引發單 體分子之自由基聚合以形成聚合物。 通吊' 在含水乳液聚合中，聚合物以分離自單體小液滴 之粒子生長。所侍之聚合物粒子令人滿意時在水中形成稱 為”膠乳”之穩定懸浮液。膠乳中之聚合物粒子稱為”膠乳粒 ” 〇 乳夜♦ο之斗夕麦化貫施於此項技術中。任何該等變化 及其組合均考慮在本發明之實施中。舉例而言，所有單體 均可存在於聚合初期，或者可在某些聚合發生後逐漸或分 V "】、' 加可在批里、半批量或連續過程中進行聚合。某些 乳，聚合可以多”階段"進行：意即在每一階段中，聚:二 種單體組合物’且接著在下_階段中添加及聚合相同或不 同之另-種單體。某些乳液聚合在單__階段中進行。 在乳液聚合之實施中，單體（意即純單體、單體之混合物 或其組合）可在聚合前或聚合期間添加至反應器中。單體可 以在反應器中進行乳/f卜，+、 或可分離乳化且接著作為乳液添 加至反應器中。可將單體或其部分以-或多批相對快速地 添加，或者可緩慢或逐漸添加，或可㈣等方法之㈣組 合添加。可在添加單體之箭 <引、過程中或之後添加引發劑。 可在添加單體之前、過程中或之後添加界面活性劑。若以 多階段進行乳液聚合’則任何上述添加單體之方法可用於 93I98.doc 1302915 任何該等階段中，且在不同階段中添加單體之方法可相同 或不同。 某些含水乳液聚合之常用實施例涉及使用至少—種"種 子。在該等實施例中，製備具有相對小膠乳粒子尺寸之膠 乳，且接著在新的聚合開始之前將相對少量之該膠乳添二 至反應器中。*於咸信該等膠乳粒子在新的聚合作用中成 為水合物生長之位置，該相對小粒子尺寸之膠乳稱為"種子,，。 有時在含水乳液聚合發生後，相對小量之單體仍然沒有 反應。在該等狀況下，可在反應器中添加某些額外引發劑 (稱為”追加劑，，）以引發未反應之單體聚合；此程序稱為"追 加"。若聚合含有一個以上階段’則在各階段間可進行一或 多個追加。在聚合過程結束時可獨立地進行一或多個追加。 在涉及乳液聚合之本發明實施例中，預期可能使用任何 =液聚合之變化’其包括上述改變，且包括該等改變之任 意組合。舉例而言’可使用任何單體加成方法；可使用任 何數目之階段；可使用或不使用種子聚合物，·可使用或不 使用追加。若使用多個階段，在任__階段中使用之乳液聚 合之變化可相同或可不同於任何其它階段中使用之乳液聚 合之變化。若使用多個階段，在任一階段中使用之單體或 單體混合物可相同或可不同於任何其它階段中使用之單體 或單體混合物。 某些含水礼液聚合之常見實施例中獨立包含膠乳之中和 乍用例如某些乳液聚合在7或更小之條件下進行，有 才希2將pH值升至大於7 ;通常藉由添加水溶性驗升高阳 93198.doc -10 - 13〇2915 值直至達到所要之pH值。 在實施本發明時，將使用之全部或幾乎全部成份選擇為 除氨化合物外之化合物。本文所用之，，氨化合物，，定義為 氨、任何含有銨離子之化合物、任何一級胺、或任何二級 月女。本文所用之”氨化合物，，不包括三級胺。 在某些實施例中，本發明之含水組合物不含或幾乎不含 氨化合物。意即氨化合物之量為零或幾乎為零。在幾乎沒 有氨化合物之某些實施例中，氨化合物之量基於該含水組 合物中聚合物之固體重量以重量計為50 ppm或更少之氨化 ^物’在其它貫施例中，該量為25 ppm或更少；或⑺p㈣ 或更少。在某些實施例中，該含水組合物中沒有氨化合物。 田氨化合物作為鹽或鹽與相應中性化合物之混合物存在 日守，本文中將氨化合物之量作為中性化合物之重量記錄。 例如办於纟中之氨有冑可描述為氨離子與氫氧離子之溶 液’·在此狀況下，本文認為溶液中之氨量為"生氨化合物 貫施本發明時，可（例如）在乳液聚合過程中使用一或多 種界面活性劑。某些乳液聚合實施例使㈣酸鹽或續酸鹽 =活性劑，·將全部或幾乎全部該等界面活性劑選為除^ 夏外之鹽；反之，可能使用鈉、鉀或其它金屬鹽。 ^實Γ發明時，有時將—或多種級劑用於含水乳液 來口，§使用一或多種引發劑時，全部或幾乎全邛所使用 之引發劑將為非氨化合物之化合物。例如可能不使 乎不使用過硫酸銨,·相反地，若須要過硫酸鹽 爾 93198.doc -11 - 1302915 何過硫酸鹽（類）將選自過硫酸金屬鹽，諸如（例如）過硫酸驗 金屬鹽(如過硫酸鈉或過硫酸鉀)。另一實例為，選擇如(例 如）非氨化合物之有機過氧化物的—或多種過氧化物作為 一或多種引發劑。 /實施本發明中’若中和膠乳’則用於調節PH之該或該 寺化合物將全部或幾乎全部選自除氨化合物以外之化合 物。舉例而言，若中和過程提高膠乳之PH，使用之鹼性化 合物可能（例如）全部或幾乎全部由—種或多種驗金屬鹽組 成，如（例如）氫氧化鈉、氫氧化鉀或其混合物。 在本發明之某些實施例中，在含水組合物中使用一或多 種緩衝劑，其有時作為乳液聚合過程之一部分。當使用一 或夕種緩衝料’將選擇使用該或該等緩衝劑以使得最終 之含水組合物不含有或幾乎不含有氨化合物。在某些實施 例中’所用每—緩衝劑皆為非氨化合物之化合物。 衣備本發明之含水組合物的方法包括為各種目的使用各 ，成份，該等成份有時包括—或多種上文提及之成份，有 或夕種其匕成份’有時包括其組合。在實施本發 明中’預期可選擇各成份以使得該成份不為氨化合物。預 期有對該等成份加以選擇之實_讀得任何特殊成份不 為氨化合物。亦預期有其中選擇成份之任意組合的實施例 以使得該組合令之各成份不為氨化合物 中全部成份不為氨化合物之實施例。 、礼、 取=貝知本發明中，在至少—種乙烯系不飽和單體上進行 K 口適口之單體為能夠經由乳液聚合形成聚合物之乙烯 93198.doc -12- 1302915 系不飽和化合物。適合之單體包括（例如）：如二稀烴、笨乙 烯之不飽和非芳香烴，其它芳香族單體，（甲基）丙烯酸單 體，及其它乙烯基單體。本文所用。之”苯乙烯”意謂苯乙烯 及諸如（例如）CK -甲基苯乙烯之苯乙烯衍生物。本文所用之 ”（甲基）丙烯酸單體”意謂任何丙烯酸、甲基丙烯酸、其酯、 及其衍生物。本文所用之，，（甲基）丙烯酸酯”意謂丙烯酸酯或 甲基丙烯酸酯。某些適合之（甲基）丙烯酸酯單體為（例 如）（甲基）丙烯酸烷酯、（甲基）丙烯酸羥烷酯及（甲基）丙烯 腈。具有（例如）如羥基或額外之乙烯基之其它功能基團的 (甲基）丙烯酸酯亦適合。某些其它適合之乙烯基單體包括 (例如）·乙烯基化合物，諸如（例如）氯乙烯、錯酸乙浠酯及 硫酸乙稀酯。適合單體之混合物亦適合。 某些適合之（甲基）丙烯酸烷酯為（如）彼等帶有2〇或更少 個石反原子之燒基的（甲基）丙烯酸烧酷。例如，某些適合之（甲 基）丙烯酸烧酯單體為（甲基）丙烯酸甲g旨、（甲基）丙晞酸正 丁酯、（曱基）丙烯酸第三丁酯、（曱基）丙烯酸2•乙基己酯、 (甲基）丙烯酸異辛酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸 硬脂酸酯、及其混合物。 在本發明之某些實施例中，該或該等聚合物由排除所有 二烯烴之單體混合物製得。某些實施例獨立地使用排除所 有丙烯腈之單體混合物；某些實施例使用排除甲基丙烯腈 ，單體混合物。本發明之某些實施例使用排除二烯烴、丙 烯腈、甲基丙烯腈之任何組合的單體混合物。 某些實施例獨立涉及至少一種聚合物，其由包括至少一 Λ 93198.doc -13- 1302915 種丙烯酸酯單體之單體混合物製得；本文中該等聚合物稱 為"含丙烯酸酯之聚合物’’。在某些含丙烯酸酯之聚合物 中，製得該聚合物之單體混合物亦含有至少一種甲基丙烯 酸酯單體。在某些含丙烯酸酯聚合物中，製得該聚合物之 單體混合物亦獨立含有丙烯酸或甲基丙烯酸或其混合物。 某些含丙烯酸酯之聚合物自含有下列單體之單體混合物製 得：1%至99%丙烯酸酯單體；〇至75%甲基丙烯酸酯單體； 0至5%丙烯酸，及0至5%甲基丙烯酸；其係以全部單體之重 量計。 由乳液承合所彳于之聚合物為膠乳聚合物。水與懸浮於其 中之膠乳聚合物粒子之組合稱為耗液。通常膠乳液為基 於全部膠乳液之重量25重量％至9〇重量％水及1〇%至75重 量％聚合物固體物。膠乳聚合物粒子通常獨立具有1〇11111至 2,000 nm之平均粒子尺寸。朦乳聚合物粒子可為球形、橢 圓形、不規則或其組合。 本發明之聚合物具有_8〇它至11〇1之玻璃轉變溫度。使 用U刀掃榣里熱计藉由中點法量測玻璃轉變溫度（丁g)。在 某些貫施例中’該聚合物將只具有-個Tg。亦預期有具有 :個玻璃轉變溫度之實施例，諸如(例如):聚合物摻合物、 多相共聚物、顯示多個玻璃轉變溫度之聚合物之其它配 置，及其組合。 、 本赉明之聚合物可具有任意寬範圍之重量平均分子重量 (MW)’其猎由尺寸排阻色譜（SEC)量測。在某些實施例中， 該含水組合你人士 ^ , 物t有至少一種具有30,000或更大Mw之聚合 93198.doc -14- 1302915 物；在其它實施例中，該至少一種聚合物具有5〇,〇〇〇或更 大、或100,000或更A、或200，_或更A、或5〇〇〇〇〇或更 大之Mw。 獨立於分子量，|發明之聚合物可為直冑、支鏈、部分 或全部經交聯、星狀、嵌段聚合物、無規聚合物，或其任 意組合。在某些實施例中’本發明之聚合物可完全不經交 如亦預期某些部分或全部之本發明之聚合物可經凝膠化 或經交聯；據預計經凝膠化及/或經交聯之部分不能藉由 SEC量測。 在成乎不含有氨化合物之本發明之某些實施例中，所存 在之少量氨由一或多種成份引入。例如可以種子聚合物引 入相對少量之氨；意即該種子聚合物可能已經使用如過硫 酸銨引發劑之氨化合物製得；通常以種子聚合物引入氨化 合物時，引入量為基於含水組合物中聚合物之總乾重以氨 化合物之重量計10 PPm或更少。再例如，本發明之含水組 e物了由§有一些氣之增稠組合物增稠；通常以增稠劑引 入氨化合物時，引入量為基於含水組合物中聚合物之總乾 重以氨化合物之重量計丨ppm或更少。第三實例為，種子及 增稠劑皆可為氨源。在實施本發明中，在該等實例或在其 它實施例中，自組合之種子及增稠劑引入含水組合物中之 氛化5物I為基於含水組合物中聚合物之總乾重以氨化合 物之重昼叶20 ppm或更少、或1〇 ρρπχ或更少。 本發明之含水組合物包括至少一種配位劑。配位劑為能 夠與金屬原子形成一或多個配位鍵之化合物。能夠與金屬 93198.doc -15- 1302915 離子形成兩個或兩個以上配位鍵之配位劑稱為螯合劑。本 發明之某些實施例涉及螯合劑之使用。Winkle在EP068 8 816 中描述某些適合之配位劑。 某些適合之配位劑包括（如）：填酸、填酸鹽及多構酸鹽。 具體之實例包括（如）：磷酸、磷酸鹽、焦磷酸鹽、三聚磷酸 鹽、六偏鱗酸鹽、四偏填酸鹽、五偏填酸鹽、及其驗金屬 鹽。其它適合之配位劑包括（如）：正膦醯基烷基正羧酸，諸 如（例如）膦醯基乙酸、2-膦醯基丁烷-1，2,4-三羧酸、2-羥基 -2-膦酸基乙酸、及其鹼金屬鹽。其它適合之配位劑包括（如） 孿-二膦酸基烷烴及孿-二膦醯基羥基烷烴，如亞甲基二膦 酸、1-經基亞乙基二膦酸、及其鹼金屬鹽。 適合之配位劑之另一群組為含有一或多個三級胺二（亞 甲基膦酸）部分之化合物的群組，其為具有下式之部分 R1 R2-C—Q R3 其中_R、-R2、及_R3獨立為氫或有機自由基，其包括烷基 自由基及經取代之有機自由基（如經基烧基自由基），且包括 將兩個或兩個以上_r1、_r2、及_r3連接至—或多個環結構 =構；且其中_Q為娜h2P〇3X2)2，其中各x獨立為氯或 欢&屬。該等化合物之具體實例包括·· 胺基參（亞甲基膦酸）， 伸乙基二胺四（亞甲基膦酸）、二伸乙基三 N,N Nr NM 7sjff ί： / τγ ，，，-(亞甲基膦酸），及其鹼金屬鹽。 93198.doc -16- 1302915 額外適合之配位劑包括例如可溶於水之具有兩個或兩個 以上懸垂（pendant)之鱗酸卓酯部分的化合物；可藉由將聚 合物功能化以含有該等懸垂之磷酸單酯部分來製備該等化 合物之某些實例；可藉由製備具有作為聚合單元之含磷酸 單酯之單體（如甲基丙烯酸磷酸乙酯、乙烯膦酸及烯丙基膦 酸）來製備其它化合物實例。其它適合之配位劑包括（如）含 有一或多個三級胺基二（亞甲基）部分之化合物，其為具有下 式之部分1302915 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to coating compositions. [Prior Art] It is often desirable to provide a coating, film or film layer having good optical properties. For example, some of the desired optical properties are transparency, no haze, and no color. A particularly desirable optical property is the relatively low gradation yellowness = and it is often desirable to maintain a relatively low gradation of yellowness during aging of the coating. Sometimes it is desirable to have good optical properties since the coating is to be applied to a substrate and it is desirable that the presence of the coating does not alter the appearance of the substrate. There is a layer coating and a substrate stacked on each other (e.g., when the coated substrate is wound into a roll)' and it is desirable that the stack thus formed have good optical properties. Two us 2002/GG82319 discloses a 2-stage emulsion polymer prepared by a sodium-based emulsifier, an initiator, a buffer 2 neutralizer, and a low content of ethyldiaminetetraacetic acid (EDTA). The problem faced by the inventors is that the aqueous agglomerate composition which can be used as a coating when dry has a lower yellowness than previously known compositions and maintains its low color Pk yellowness upon aging. We have found that this problem can be solved by providing an aqueous polymer composition which excludes all or almost all of the constituents from the composition and which comprises a sufficient amount of at least one complexing agent in the composition. . SUMMARY OF THE INVENTION In a first aspect of the invention, there is provided a method of preparing an aqueous composition suitable for use as a coating when dried, comprising: 93198.doc 1302915 U) providing at least one aqueous poly occupant ^ ^ ^ ^ a substance which is prepared by polymerization of at least one ethylenically unsaturated precursor and having a glass transition temperature of -8 (TC to 11 〇t, and (b) addition based on the at least one The dry weight of the λ κ hydrate is at least 1 〇 ppm by weight of at least one complexing agent, and the medium έ hydrophobic composition contains 〇 to 1 重量 by weight based on the dry weight of the polymer Ammonia compound. In a second aspect of the invention, there is provided a process for the preparation of an aqueous composition suitable for use as a coating when dried, comprising: (a) providing at least one aqueous polymer saturated monomer Polymerization to produce a variable temperature, and 'by adding at least one ethylene-free glass having a temperature of -80 ° C to 110 ° C (b) adding at least 卯 based on the dry weight of the at least one polymer At least one complexing agent, wherein the preparation of the aqueous composition The component used in the present invention does not comprise an ammonia compound. In a third aspect of the invention, there is provided an aqueous composition suitable for use as a coating when dried, comprising: (a) at least one aqueous polymer by at least one A polymerization of a vinyl-based unsaturated monomer prepared and having a glass transition temperature of from -80 ° C to 11 ° C, (b) at least 10 ppm by weight of at least one complexing agent based on the dry weight of the at least one polymer And (C) hydrating to 1 〇〇ρριη ammonia compound based on the dry weight of the at least one polymer. [Embodiment] 93198.doc 1302915 The coating used herein is applied to one or more layers of a substrate. The coating may have any of several purposes including, for example, protecting a substrate, decorating a substrate, adhering two or more substrates together, sealing a substrate, cracking in a filled substrate, other uses thereof, or The coating may be a continuous or discontinuous layer; the coating may be relatively thin or relatively thick. The practice of the present invention relates to the use of an aqueous polymer carried in an aqueous medium. ''Loaded in '' It is meant to be dissolved, dispersed, suspended, supported, or any combination thereof. The aqueous medium is typically at least 50% by weight water, or at least 75% by weight water, or at least 90% by weight water, based on the weight of the medium. In certain embodiments, the aqueous polymer is prepared by solution polymerization, suspension polymerization, emulsion polymerization, or a combination thereof in an aqueous medium. In certain embodiments, the aqueous polymer is produced outside of an aqueous medium (eg, The aqueous polymer is formed by solution polymerization in a non-aqueous solvent or by bulk polymerization and then combined with an aqueous medium. In certain embodiments, aqueous emulsion polymerization is known by the art (eg, The aqueous polymer was prepared by MS El-Aasser and ED Sudol, as described by PA Lovell and MS El-Aasser, as described in Chapter 2 of Emulsion Polymerization and Emulsion Polymers, published by John Wiley and Sons, 1997. Aqueous emulsion polymerization involves the formation of a monomer droplet emulsion (i.e., "emulsification" of the monomer) in an aqueous medium in a reactor, which is typically stabilized by the presence of at least one surfactant. The monomer used in the aqueous emulsion polymerization is a compound capable of participating in radical polymerization. The monomer droplets may contain a single monomer or a mixture of monomers. One or more initiators are used in most aqueous emulsion polymerization processes. Trigger 93198.doc 1302915 ^ for some people who believe that in response to elevated temperatures, chemical reactions or radiation (such as light 2, electrons, gamma rays, or a combination thereof), some of the stimuli produce free radicals. The agent is a persulfate. Other commonly used initiators are 4 and ..., organic peroxides. It is believed that the free radicals produced by the initiator initiate free radical polymerization of the monomer molecules to form a polymer. Through-watering In aqueous emulsion polymerization, the polymer grows as particles separated from small droplets of monomer. When the polymer particles are satisfactory, a stable suspension called "latex" is formed in water. The polymer particles in the latex are called "latex particles" 〇 Milky nights ♦ ο 之 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦 麦Any such variations and combinations thereof are contemplated in the practice of the invention. For example, all of the monomers may be present at the beginning of the polymerization, or may be polymerized in batch, semi-batch or continuous processes after some polymerization has occurred. For some milks, the polymerization can be carried out in multiple "stages": meaning that in each stage, poly: two monomer compositions' and then in the next stage add and polymerize the same or different other monomers. Some emulsion polymerizations are carried out in a single stage. In the practice of emulsion polymerization, monomers (meaning pure monomers, mixtures of monomers or combinations thereof) can be added to the reactor before or during the polymerization. Milk/f, +, or emulsifiable emulsification can be carried out in the reactor and the emulsion can be added to the reactor. The monomer or part thereof can be added relatively quickly in - or batches, or can be added slowly or gradually Or (4) may be added in combination. The initiator may be added during the addition of the arrow of the monomer. The surfactant may be added before, during or after the addition of the monomer. Performing emulsion polymerization' then any of the above methods of adding monomers can be used in any of these stages of 93 I98.doc 1302915, and the method of adding monomers in different stages can be the same or different. Common examples of certain aqueous emulsion polymerizations involve At least one seed is used. In these embodiments, a latex having a relatively small latex particle size is prepared, and then a relatively small amount of the latex is added to the reactor before the start of the new polymerization. The latex particles become the location of hydrate growth in the new polymerization, and the latex of the relatively small particle size is called "seed.] Sometimes a relatively small amount of monomer still does not react after the aqueous emulsion polymerization occurs. Under these conditions, some additional initiator (referred to as "adder,") may be added to the reactor to initiate polymerization of the unreacted monomer; this procedure is referred to as "addition". If the polymerization contains more than one stage, then one or more additions can be made between the stages. One or more additions can be made independently at the end of the polymerization process. In embodiments of the invention involving emulsion polymerization, it is contemplated that any change in = liquid polymerization may be used, which includes the above-described changes, and includes any combination of such changes. For example, any monomer addition method can be used; any number of stages can be used; seed polymers can be used with or without, and may or may not be used. If multiple stages are used, the change in emulsion polymerization used in any of the stages may be the same or may vary from the change in emulsion polymerization used in any other stage. If multiple stages are used, the monomer or monomer mixture used in either stage may be the same or may be different from the monomer or monomer mixture used in any other stage. In some common examples of aqueous liquor polymerization, the latex is included separately and the hydrazine is carried out, for example, under some conditions of 7 or less, and the pH is raised to greater than 7; usually by adding The water solubility test increases the value of 93918.doc -10 - 13〇2915 until the desired pH is reached. In carrying out the invention, all or almost all of the components used are selected as compounds other than the ammonia compound. As used herein, an ammonia compound, defined as ammonia, any compound containing an ammonium ion, any primary amine, or any secondary female. As used herein, an ammonia compound, excluding a tertiary amine. In certain embodiments, the aqueous compositions of the present invention are free or nearly free of ammonia compounds, meaning that the amount of ammonia compound is zero or nearly zero. In some embodiments in which there is little ammonia compound, the amount of ammonia compound is 50 ppm by weight or less based on the weight of the solids of the polymer in the aqueous composition. In other embodiments, the amount 25 ppm or less; or (7) p (four) or less. In certain embodiments, there is no ammonia compound in the aqueous composition. The field ammonia compound is present as a salt or a mixture of a salt and a corresponding neutral compound, which will be The amount of ammonia compound is recorded as the weight of the neutral compound. For example, the ammonia in the sputum can be described as a solution of ammonia ion and hydroxide ion ion. · In this case, the amount of ammonia in the solution is considered to be " When the ammonia compound is applied to the present invention, one or more surfactants can be used, for example, in the emulsion polymerization process. Some emulsion polymerization examples give (tetra) acid salts or acid salts = active agents, all or almost all The surfactant is selected as the salt other than Xixia; on the contrary, sodium, potassium or other metal salts may be used. ^In the case of the invention, sometimes - or a plurality of grades are used for the aqueous emulsion, § use one or In the case of a plurality of initiators, the initiator used in all or almost all of the ruthenium will be a compound of a non-ammonia compound. For example, ammonium persulfate may not be used, and conversely, if persulfate is required, 93,998.doc -11 - 1302915 The persulfate (class) will be selected from metal salts of persulfate, such as, for example, a persulfate metal salt (such as sodium persulfate or potassium persulfate). Another example is the selection of, for example, a non-ammonia compound. Organic peroxide- or a plurality of peroxides as one or more initiators. /In the practice of the invention, 'if neutralizing latex' is used to adjust the PH or the compound of the temple will be wholly or almost all selected from the ammonia-removing compound. For example, if the neutralization process increases the pH of the latex, the basic compound used may, for example, consist entirely or almost entirely of one or more metal salts, such as, for example, sodium hydroxide, hydroxide Potassium Mixtures. In certain embodiments of the invention, one or more buffering agents are used in the aqueous composition, which are sometimes part of the emulsion polymerization process. When using one or a kind of buffering agent, the The buffer is such that the final aqueous composition contains no or substantially no ammonia compound. In some embodiments, each of the buffers used is a non-ammonia compound. The method of preparing the aqueous composition of the present invention includes The use of ingredients, ingredients, etc., sometimes includes - or a plurality of the above-mentioned ingredients, sometimes or in the form of a combination thereof, sometimes including combinations thereof. In the practice of the invention, it is contemplated that the ingredients may be selected The composition is not an ammonia compound. It is expected that the components are selected. It is understood that any particular component is not an ammonia compound. It is also contemplated that there are embodiments in which any combination of components is selected such that the components are not It is an example in which all components in the ammonia compound are not ammonia compounds. In the present invention, the monomer having a K-port in the at least one type of ethylenically unsaturated monomer is ethylene 93998.doc -12-1302915 unsaturated compound capable of forming a polymer via emulsion polymerization. . Suitable monomers include, for example, dibasic hydrocarbons, ethylenically unsaturated non-aromatic hydrocarbons, other aromatic monomers, (meth)acrylic monomers, and other vinyl monomers. Used in this article. "Styrene" means styrene and a styrene derivative such as, for example, CK-methylstyrene. As used herein, "(meth)acrylic monomer" means any acrylic acid, methacrylic acid, esters thereof, and derivatives thereof. As used herein, (meth) acrylate means acrylate or methacrylate. Some suitable (meth) acrylate monomers are, for example, alkyl (meth) acrylate, (methyl) Hydroxyalkyl acrylates and (meth)acrylonitriles. (Meth) acrylates having, for example, other functional groups such as hydroxyl groups or additional vinyl groups are also suitable. Certain other suitable vinyl monomers include (for example Vinyl compounds such as, for example, vinyl chloride, ethyl decanoate and ethyl sulphate. Suitable mixtures of monomers are also suitable. Certain suitable alkyl (meth) acrylates are, for example, (meth)acrylic acid having 2 or less of a stone anti-atomic group. For example, some suitable (meth)acrylic acid ester monomers are (meth)acrylic acid, (methyl) N-butyl propionate, tert-butyl (meth)acrylate, 2·ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, (methyl) Acrylic stearate, and mixtures thereof. In the present invention In certain embodiments, the or the polymers are prepared from a monomer mixture that excludes all diolefins. Certain embodiments independently use a monomer mixture that excludes all acrylonitrile; some embodiments use methacrylonitrile to exclude , monomer mixtures. Certain embodiments of the invention use monomer mixtures that exclude any combination of diolefins, acrylonitrile, methacrylonitrile. Certain embodiments independently relate to at least one polymer comprising at least one Λ 93198 .doc -13- 1302915 A monomer mixture of acrylate monomers; these polymers are referred to herein as "acrylate-containing polymers'. In certain acrylate-containing polymers, The monomer mixture of the polymer also contains at least one methacrylate monomer. In some acrylate-containing polymers, the monomer mixture from which the polymer is made also independently contains acrylic acid or methacrylic acid or a mixture thereof. Some acrylate-containing polymers are prepared from a monomer mixture containing the following monomers: 1% to 99% acrylate monomer; 〇 to 75% methacrylate monomer; 0 to 5% acrylic acid, And 0 to 5% methacrylic acid; which is based on the weight of all monomers. The polymer to which the emulsion is supported is a latex polymer. The combination of water and latex polymer particles suspended therein is called a liquid consumption. Typically, the latex is from 25% to 9% by weight water and from 1% to 75% by weight polymer solids based on the weight of the total latex. The latex polymer particles typically have an average particle size of from 1 to 11111 to 2,000 nm. The emulsion polymer particles may be spherical, elliptical, irregular, or a combination thereof. The polymer of the present invention has a glass transition temperature of from 〇8 〇 to 11 。 1. Using a U knife broom heat meter by the midpoint method The glass transition temperature (dg) is measured. In some embodiments, the polymer will have only one Tg. Embodiments having a glass transition temperature, such as, for example, polymer blending, are also contemplated. Other configurations of heterogeneous copolymers, polymers exhibiting multiple glass transition temperatures, and combinations thereof. The polymers of the present invention can have any wide range of weight average molecular weights (MW)' which are measured by size exclusion chromatography (SEC). In certain embodiments, the aqueous combination has a polymer of 93198.doc -14 - 1302915 having at least one Mw of 30,000 or greater; in other embodiments, the at least one polymer has 5 〇. , 〇〇〇 or greater, or 100,000 or more, or 200, _ or A, or M 。 or greater. Independent of molecular weight, the inventive polymer can be straight, branched, partially or fully crosslinked, star shaped, block polymer, random polymer, or any combination thereof. In certain embodiments, the polymer of the present invention may be completely untreated, and it is contemplated that some or all of the polymers of the present invention may be gelled or crosslinked; it is expected to be gelled and/or The cross-linked portion cannot be measured by SEC. In certain embodiments of the invention that are free of ammonia compounds, the small amount of ammonia present is introduced by one or more components. For example, a relatively small amount of ammonia can be introduced into the seed polymer; that is, the seed polymer may have been prepared using an ammonia compound such as an ammonium persulfate initiator; typically when the seed polymer is introduced into the ammonia compound, the amount of introduction is based on the aqueous composition. The total dry weight of the polymer is 10 ppm or less based on the weight of the ammonia compound. Further, for example, the aqueous group of the present invention is thickened by a thickening composition having some gas; usually, when the ammonia compound is introduced as a thickener, the amount is introduced based on the total dry weight of the polymer in the aqueous composition. The weight of the compound is 丨 ppm or less. In a third example, both the seed and the thickener can be ammonia sources. In the practice of the invention, in such examples or in other embodiments, the self-combining seed and thickener are incorporated into the aqueous composition. The aerosolized material I is based on the total dry weight of the polymer in the aqueous composition. The heavy leaf of the compound is 20 ppm or less, or 1 〇ρρπχ or less. The aqueous composition of the present invention comprises at least one complexing agent. The complexing agent is a compound capable of forming one or more coordinate bonds with a metal atom. A complexing agent capable of forming two or more coordinate bonds with a metal 93198.doc -15-1302915 ion is referred to as a chelating agent. Certain embodiments of the invention relate to the use of a chelating agent. Winkle describes certain suitable complexing agents in EP068 8 816. Some suitable complexing agents include, for example, acid-filling, acid-filling, and polystructuring salts. Specific examples include, for example, phosphoric acid, phosphate, pyrophosphate, tripolyphosphate, hexametaphosphate, tetra-salt acid salt, penta-partic acid salt, and metal salts thereof. Other suitable complexing agents include, for example: n-phosphinodecylalkyl ortho carboxylic acids such as, for example, phosphinic acid, 2-phosphonium butane-1,2,4-tricarboxylic acid, 2- Hydroxy-2-phosphonic acid acetic acid, and alkali metal salts thereof. Other suitable complexing agents include, for example, fluorene-diphosphonic alkanes and hydrazine-diphosphinyl hydroxyalkanes such as methylene diphosphonic acid, 1-transethylidene diphosphonic acid, and alkali metals thereof. salt. Another group of suitable complexing agents is a group of compounds containing one or more tertiary amine bis(methylenephosphonic acid) moieties which are part of the formula R1 R2-C-Q R3 wherein _ R, -R2, and _R3 are independently hydrogen or an organic radical, which includes an alkyl radical and a substituted organic radical (such as a carbyl radical), and includes two or more _r1 , _r2, and _r3 are attached to - or a plurality of ring structures = structure; and wherein _Q is Na h2P 〇 3X2) 2, wherein each x is independently a chlorine or a genus. Specific examples of such compounds include: an amine ginseng (methylene phosphonic acid), an ethyl diamine tetra (methylene phosphonic acid), a diethylidene tri N, N Nr NM 7sjff ί: / τγ , ,, - (methylene phosphonic acid), and its alkali metal salt. 93198.doc -16- 1302915 Additional suitable complexing agents include, for example, water-soluble compounds having two or more pendant oleic acid ester moieties; functionalized by the polymer to contain These pendant phosphoric acid monoester moieties are used to prepare certain examples of such compounds; by preparing a monomer having a phosphoric acid monoester as a polymerized unit (e.g., ethyl methacrylate, vinylphosphonic acid, and allyl) Phosphonic acid) to prepare examples of other compounds. Other suitable complexing agents include, for example, compounds containing one or more tertiary amino bis(methylene) moieties which are part of the formula
其中-R1、-R2、及-R3如上文所定義，且小為_n(CH2C〇2X)2， 且其中各X獨立為氫或鹼金屬。該等化合物之具體實例包 括· N-(2-經乙基）伸乙基二胺三乙酸、伸乙基二胺四乙酸、 腈基參（亞甲基魏酸）、及其驗金屬鹽。當配位劑具有每分子 多於一個酸基時，應瞭解”其鹼金屬鹽”包括其中自一個酸 基團形成驗金屬鹽之化合物，其中自多於一個酸基團形成 鹼金屬鹽之化合物；及其混合物及組合。在某些實施例中， 該等鹼金屬鹽為鈉鹽。 適合之配位劑之混合物亦為適合之配位劑。 在某些實施例中，一或多種配位劑以一定含量存在以使 得全部配位劑之重量為基於聚合物之乾重10卯以或更大。 在其它實施例中，（多種）配位劑之重量基於聚合物之乾重為 25 ppm或更大；或50 ppm或更大；或1〇〇 ppnl或更大；或250 ppm或更大，或500 ppm或更大；或1〇〇〇 ppm或更大。在某 93198.doc 1302915 些實施例t，配位劑之重量基於聚合物之乾重獨立為 2〇，咖ppm或更小，《10,000 ppm或更小，或5〇〇〇啊或 更小，或2,000 ppm或更小。 雖然本發明不受任何特殊機制限制，❻由於存在可為 (如）純金屬或合金、金屬氧化物、金屬鹽或其混合物之一或 多種含金屬化合物，咸信某些塗層傾向於具有黃色，或隨 著老化逐步變成黃色。被認為通常促進塗層中形成不希望 之顏色的金屬包括（如）鐵及鋼。在促進形成不希望之顏色 上，據認為除鹼金屬外之金屬比鹼金屬更有效。 舉例而言，若含鐵化合物存在於本發明之組合物中，則 它可自多種來源引入該組合物中。它可能是（例如）在製備聚 合物過程中被有意引入催化劑中或作為氧化/還原系統之 一部分。亦可（例如）自製備、運輸或存儲聚合物、組合物中 之其它成份或整個組合物中所使用之管道或反應器引入該 含鐵化合物。該含鐵化合物亦可（例如）以作為一或多種原料 中之雜質的方式引入該組合物中。該含鐵化合物亦可自其 上塗有聚合物之基板引入該組合物，或自可選用之至少一 種顏料中引入。當含鐵化合物存在於本發明之組合物中 時，有時發現它們的含量基於該聚合物之乾重以重量計為 1 ppm或更大且有時為2 ppm或更大。有時本發明組合物中 含鐵化合物之存在量基於該聚合物之乾重以重量計獨立為 1〇,〇〇〇?0111或更小，且有時存在量為5,〇〇〇1)1)111或更小。 在本發明之某些實施例中，本發明之含水組合物將包括 某些非驗金屬原子，例如在乳液聚合過程中作為引發劑之 93198.doc -18- 1302915 一部分所引入之鐵原子。在某些該等實施例中，該至少一 種配位齊1的存在量足以提供超過非驗金屬原子之莫耳過量 配位劑；例如配位劑與非金屬原子之莫耳比為至少1 : ^、 或至少2: 1、或至少3:丨、或至少5:丨、或至少丨㈧卜在 具有超過非鹼金屬原子之莫耳過量配位劑之實施例中，據 認為該過量配位劑能夠與可引入該組合物（例如自管道或 罐中）之任何非鹼金屬原子相互作用，由此阻止不希望之顏 色的形成。 在某些實施例中，本發明之組合物含有至少一種，，澄清，， 配位劑（即減小含有非驗金屬之組合物的可見光譜吸收度 之配位劑）。可藉由將配位劑添加至含有非鹼金屬（如鐵）之 組合物中，且量測在可見光譜中吸收度之減小來將其識別 為澄清配位劑；進行吸收度測試之組合物可為亦可作為塗 層之組合物、或者進行吸收度測試之組合物可為經選擇具 有易里測之吸收光譜的測試組合物。在本發明之某此實施 例中，所用各配位劑為澄清配位劑。纟本發明之某些實施 J中所用各配位劑將不為澄清配位劑。在本發明之某些 貝施例中，將使用一或多種澄清配位劑之混合物及一或多 種其它配位劑。 除了所預期之配位劑與非鹼金屬原子間之相互作用外， 口人亦已發現本發明之組合物具有令人驚奇之低色階黃 度，且令人驚奇地善於阻止在老化期間黃度之出現，甚至 在非驗金屬量很低或為零之含水組合物中。 對於本發明而言，添加該至少一種配位劑之時間並不重 93198.doc -19- 1302915 要。可在聚合之前、聚合過程令、聚合之後或在其組合中 添加該至少-種配位劑。例如，可將該至少一種配位劑作 為-或多種聚合組份之-種組份分開引入、或作為其任意 ’’且口引入。在某些貫施例中，在聚合物聚合完成後引入該 至少-種配位劑。在某些獨立實施例中，在酸性pH時添加 該至少-種配位劑。在本發明之一特定實施例中，在酸性 PH下進行乳液聚合，在聚合完成後將該至少一種配位劑添 加至膠乳中，且接著將該膠乳令和至鹼性pH。 本發明之組合物可視情況含有額外成份，其通常為用以 改善所要塗層種類之特性的佐劑。該等佐劑之實例包括一 或多種（如）著色劑、增稍劑、聚結劑 料、填料、濕潤劑、界面活性劑、及分散劑。在^本; 明中’將選擇該等額外成份以使得該含水、组合物沒有或幾 乎沒有氨化合物。 在某些含有-或多種該等額外成份之實施例中，選擇該 等添加成份以使得該至少一種額外成份不為氨化合物。例 如’在某些含有消泡劑之實施例中，該經選擇之消泡劑不 為氨化合物。在某些實施例中，該等成份中沒有氨化合物。 本發明之組合物可藉由大量方法中之任何方法施用於-或多個基板上。在包括（例如）噴^、刷塗、噴霧式塗覆、浸 潰塗覆、滾塗、壓光、槽縫式塗覆、簾幕式塗覆、以繞線 棒塗覆及擦拭之某些適合之施用方法中，將該含水組合物 施用於基板上且接著使該含水介質蒸發或允許其蒸發。在 其它合適之施用方法中，藉由（如）噴霧乾燥或凝固隨後進行 93198.doc -20- 1302915 乾燥自3亥含水組合物之剩餘成份中分離含水介質，且接著 在通常包含加熱該等剩餘成份且將所得熔融物適用於基板 之過程中將剩餘成份施用於一或多個基板上。施用於基板 之後，該組合物可進行或不進行進一步加熱。施用於基板 後，5亥組合物可獨立地經受或不經受進一步化學反應，諸 如（例如）固化及交聯反應。若任何或全部以下原因關係到特 殊類型之塗層則據估計將希望在施用後加熱塗層··當要求 快速乾燥時，當希望且要求進一步之化學反應時；及當某 些或全部之該至少一種聚合物為具有高於室溫之Tg的聚合 物時。 本發明之含水組合物可作為塗層施用於任何一或多種寬 範圍之基板。基板可為例如金屬（諸如（例如）鐵、鋼或鋁）、 木材、水泥質物質（如混凝土、灰聚或灰泥）、塑料（諸如（例 如）聚氣乙烯、聚苯乙烯、聚碳酸酯、聚酯、聚烯烴、或其 它塑料）、礦物、纖維（諸如（例如）紙、無紡織物、或紡織織 物）、纖維（諸如（例如）纖維二乙酸酯）、或其任意組合。在 某些狀況下，一種或多種基板將相對較厚，諸如（例如）建築 之結構件，如金屬工字梁（I-beam)或木柱。在某些狀況下， 一或多種基板將相對較薄’諸如（例如）金屬箔（諸如（例如） 鋁箔）、紙、布、纖維薄膜、或塑料薄膜（諸如（例如）聚酯或 聚丙烯薄膜）。 一種評價塗層黃度之方法為量測CIE L*a*b色彩空間之 ”b”參數。增加之正b值表明增加之黃度。可藉由三原色比 色5十（亦稱為色度计）ϊ測b蒼數。該b蒼數及其含義在此項技 1302915 術中為人所知，其彳田述於例如BiUmeya及Saitzman之 Principles of Color Techn〇1〇gy，第二版，j〇hn wney & 3刪， 1981 中。 應瞭解為本發明說明書及申請專利範圍之目的，可組合 本文列舉之範圍及比例限制。例如，若對於一具體參數列 舉60至120及80至11〇之範圍，應瞭解亦應預期6〇至11〇及8〇 至120之範圍。若獨立地將具體參數之最小值列舉為（如y、 2或3,且若亦獨立地將該參數之最大值列舉為（如〉8及9,則 應預期全部以下範圍：1至8、1至9、2至8、2至9、3至8、 及3至9。 實例 在下列各實例中，使用了兩種中和膠乳之不同方法中的 一種： ⑴氨·將以重量計水與濃氨水之1比1混合物添加至膠乳直 至pH達到7.5。 (η) NaOH ·將以重量計5%之氫氧化鈉水溶液添加至膠乳直至 pH達到7.5。 在下列實例中，縮寫"CA”係指Dequest™ 2016, 一種含有 約20.5%(1-羥基亞乙基）二膦酸、鈉鹽、及〇_2%膦酸氫二鈉 (可自Solutia，Inc購得）之水溶液。 在下列各實例中，使用了三種含量之CA之一種：〇、1 80 ppm之CA、或365 ppm之ca(基於該聚合物之乾重以重量 計）。 在下列各實例中，將兩種含量之硫酸鐵中之一種添加至 93198.doc -22- 1302915 含水組合物中。將鐵量記錄為以聚合物之乾重計的ppm。所 使用之含量為〇或6 ppm之鐵。 在下列實例中，以Minolta色度計CR-200(本文中，為，，色 度计π)如下量測塗層之黃度。將該含水組合物塗覆於厚度 為 50.8 μιη(2 mil)之聚酉旨薄片（Mylar™ from DuPont Co·)上 且在強制送風烘箱中於l〇5°C下乾燥3分鐘。塗層光滑、平 整、潔淨且沒有缺陷，其厚度為38.i gmG.5 mil) 土 25 μπι(〇1 mi1) °使用橡膠滾筒將第二片聚酯薄膜層壓至該塗層上。將 所得層壓板切成8片，其相互堆疊至頂層以製得測試樣品。 根據薇商說明書將色度計之Yxy色彩空間校正至標準白 底’且接著量測該測試樣品之b值且記錄為，，未經老化，，之b 值。接著將該測試樣品置放於強制通風爐中在15〇aC下15 刀名里自爐中移出’冷卻至室溫，且再次量測b值，此次記 為”經老化"之b值。 亦使用相同方法將未經老化及經老化之無任何塗層之聚 酉旨薄膜的16片堆疊作為對照樣品以色度計測試。 實例U膠乳聚合物LP1 按下列方式製備膠乳聚合物（LP1):將890 g去離子水注入 一爸中且加熱至89°C。下一步向該釜中添加22 g水中之0.9 g 碳酸納、34 g水中之4.0 g過硫酸鈉及30 g具有1〇〇毫微米粒 子尺寸之45%固形物丙浠酸膠乳聚合物之混合物外加3〇 g 水沖洗。控制5分鐘後，將475 g水、17.4 g十二烷基苯磺酸 納（23%)、1〇〇〇 g丙烯酸丁酯、980 g甲基丙烯酸甲酯、及20 g 丙烯酸之單體乳液混合物與含有1〇 g過硫酸鈉水（9() g)溶 93198.doc -23- 1302915 液之共進料一起經三個半小時缓慢加入爸中，隨後進行33 g 水沖洗。在添加進料過程中，蒼溫維持在8 6 °C。進料完成 後30分鐘時，將釜冷卻至60°C，且添加16.7 g 0.15%硫酸亞 鐵（II)溶液，隨後進行兩次追加，每次由5.6 g水中之1.2 g 第三丁基過氧化氫、及13.3 g水中之0.72 g甲醛次硫酸氫 納。在添加第二個追加劑後，將該爸冷卻至40°C以下。 實例2_5 :含水組合物 使用了膠乳聚合物LP1製得下列實例之含水組合物。 實例# 中和 ppm CA ppm Fe 0 5 0 5 8 6 8 6 11 3 11 3 0 0 6 6Wherein -R1, -R2, and -R3 are as defined above, and are as small as _n(CH2C〇2X)2, and wherein each X is independently hydrogen or an alkali metal. Specific examples of such compounds include N-(2-ethyl)-extended ethyldiaminetriacetic acid, ethylidenediaminetetraacetic acid, nitrile-based (methylene-weilic acid), and metal salts thereof. When the complexing agent has more than one acid group per molecule, it should be understood that "the alkali metal salt thereof" includes a compound in which a metal salt is formed from an acid group, and a compound which forms an alkali metal salt from more than one acid group. ; and mixtures and combinations thereof. In certain embodiments, the alkali metal salt is a sodium salt. Mixtures of suitable complexing agents are also suitable as complexing agents. In certain embodiments, the one or more complexing agents are present in an amount such that the total weight of the complexing agent is 10 Torr or greater based on the dry weight of the polymer. In other embodiments, the weight of the complexing agent(s) is 25 ppm or greater based on the dry weight of the polymer; or 50 ppm or greater; or 1 〇〇ppnl or greater; or 250 ppm or greater, Or 500 ppm or more; or 1 〇〇〇 ppm or more. In some of the examples 93108.doc 1302915, the weight of the complexing agent is independently 2 〇 based on the dry weight of the polymer, 10,000 ppm or less, 10,000 ppm or less, or 5 Å or less, Or 2,000 ppm or less. Although the invention is not limited by any particular mechanism, certain coatings tend to have a yellow color due to the presence of one or more metal-containing compounds which may be, for example, pure metals or alloys, metal oxides, metal salts or mixtures thereof. Or gradually turn yellow as the aging progresses. Metals believed to generally promote the formation of undesirable colors in the coating include, for example, iron and steel. In promoting the formation of undesirable colors, it is believed that metals other than alkali metals are more effective than alkali metals. For example, if an iron-containing compound is present in the compositions of the present invention, it can be incorporated into the composition from a variety of sources. It may be, for example, intentionally introduced into the catalyst during the preparation of the polymer or as part of an oxidation/reduction system. The iron-containing compound can also be introduced, for example, from a pipe or reactor used in the preparation, transport or storage of the polymer, other ingredients in the composition, or the entire composition. The iron-containing compound can also be introduced into the composition, for example, as an impurity in one or more of the starting materials. The iron-containing compound may also be introduced into the composition from a substrate on which the polymer is applied, or may be introduced from at least one of the pigments that may be used. When iron-containing compounds are present in the composition of the present invention, they are sometimes found to be contained in an amount of 1 ppm by weight or more based on the dry weight of the polymer and sometimes 2 ppm or more. Sometimes the iron-containing compound in the composition of the present invention is present in an amount of 1 Å by weight, based on the dry weight of the polymer, 〇〇〇?0111 or less, and sometimes present in an amount of 5, 〇〇〇1) 1) 111 or less. In certain embodiments of the invention, the aqueous compositions of the present invention will comprise certain non-tested metal atoms, such as iron atoms introduced as part of 93198.doc -18-1302915 as an initiator during emulsion polymerization. In certain such embodiments, the at least one coordination level is present in an amount sufficient to provide a molar excess complexing agent over the non-metal atom; for example, the molar ratio of the complexing agent to the non-metal atom is at least 1: ^ , or at least 2: 1, or at least 3: 丨, or at least 5: 丨, or at least 丨 (8) 卜 in an embodiment having a molar excess complexing agent over a non-alkali metal atom, the excess complexing agent is believed to be It is capable of interacting with any non-alkali metal atom that can be introduced into the composition (e.g., from a pipe or tank), thereby preventing the formation of undesirable colors. In certain embodiments, the compositions of the present invention contain at least one, clear, complexing agent (i.e., a complexing agent that reduces the absorbance of the visible spectrum of the composition containing the non-metallecturizing agent). It can be identified as a clear complexing agent by adding a complexing agent to a composition containing a non-alkali metal such as iron, and measuring the decrease in absorbance in the visible spectrum; performing a combination of absorbance tests The composition may be a composition that may also be used as a coating, or a composition for performing an absorbance test, which may be a test composition selected to have an absorbance spectrum that is easy to measure. In one such embodiment of the invention, each of the complexing agents used is a clear complexing agent. Each of the complexing agents used in certain embodiments of the present invention will not be a clearing complexing agent. In some of the examples of the present invention, a mixture of one or more clearing complexing agents and one or more other complexing agents will be used. In addition to the expected interaction between the complexing agent and the non-alkali metal atom, it has been found that the compositions of the present invention have surprisingly low gradation yellowness and are surprisingly good at preventing yellowing during aging. The degree of occurrence, even in aqueous compositions where the amount of non-metallized metal is very low or zero. For the purposes of the present invention, the addition of the at least one complexing agent does not amount to 93198.doc -19-1302915. The at least one complexing agent may be added before polymerization, after the polymerization process, after the polymerization, or in a combination thereof. For example, the at least one complexing agent may be introduced as a component of - or a plurality of polymeric components separately, or as any of them. In some embodiments, the at least one complexing agent is introduced after the polymerization of the polymer is completed. In certain independent embodiments, the at least one complexing agent is added at an acidic pH. In a particular embodiment of the invention, the emulsion polymerization is carried out at an acidic pH, the at least one complexing agent is added to the latex after the polymerization is completed, and then the latex is allowed to neutralize to an alkaline pH. The compositions of the present invention may optionally contain additional ingredients which are typically adjuvants to improve the characteristics of the type of coating desired. Examples of such adjuvants include one or more of, for example, colorants, extenders, coalescents, fillers, wetting agents, surfactants, and dispersing agents. The additional ingredients will be selected in such a way that the aqueous, composition has no or substantially no ammonia compound. In some embodiments containing - or more of the additional ingredients, the additional ingredients are selected such that the at least one additional ingredient is not an ammonia compound. For example, in some embodiments containing an antifoaming agent, the selected antifoaming agent is not an ammonia compound. In certain embodiments, there are no ammonia compounds in the components. The compositions of the present invention can be applied to - or multiple substrates by any of a number of methods. Including, for example, spraying, brushing, spray coating, dip coating, roll coating, calendering, slot coating, curtain coating, coating with a wire bar and wiping In a suitable method of application, the aqueous composition is applied to a substrate and the aqueous medium is then allowed to evaporate or allowed to evaporate. In other suitable methods of application, the aqueous medium is separated from the remaining components of the aqueous composition of the 3H by, for example, spray drying or solidification followed by drying of 93,198.doc -20 - 1302915, and then typically including heating the remainder The components are applied to one or more substrates during the application of the resulting melt to the substrate. After application to the substrate, the composition may or may not be further heated. After application to the substrate, the 5 liter composition can be independently or not subjected to further chemical reactions such as, for example, curing and crosslinking reactions. If any or all of the following reasons relate to a particular type of coating, it is estimated that it will be desirable to heat the coating after application, when rapid drying is desired, when further chemical reactions are desired and required; and when some or all of At least one of the polymers is a polymer having a Tg above room temperature. The aqueous compositions of the present invention can be applied as a coating to any one or more of a wide range of substrates. The substrate can be, for example, a metal such as, for example, iron, steel or aluminum, wood, cementitious materials such as concrete, ash or plaster, plastics such as, for example, polyethylene, polystyrene, polycarbonate. , polyester, polyolefin, or other plastic), mineral, fiber (such as, for example, paper, nonwoven, or woven fabric), fiber (such as, for example, fiber diacetate), or any combination thereof. In some cases, one or more of the substrates will be relatively thick, such as, for example, structural members of a building, such as metal I-beams or wood beams. In some cases, one or more substrates will be relatively thin 'such as, for example, a metal foil (such as, for example, aluminum foil), paper, cloth, fiber film, or plastic film (such as, for example, a polyester or polypropylene film). ). One method of evaluating the yellowness of a coating is to measure the "b" parameter of the CIE L*a*b color space. Increasing the positive b value indicates an increased yellowness. The b-number can be measured by the three primary color ratios (also known as the colorimeter). The b-number and its meaning are known in the art of 1302915, and the field is described in, for example, BiUmeya and Saitzman's Principles of Color Techn〇1〇gy, second edition, j〇hn wney & In 1981. It is to be understood that the scope and proportions set forth herein may be combined for the purpose of the invention and the scope of the claims. For example, if a range of 60 to 120 and 80 to 11 列 is listed for a particular parameter, it should be understood that ranges of 6 〇 to 11 〇 and 8 至 to 120 should also be expected. If the minimum value of a specific parameter is independently listed as (such as y, 2 or 3, and if the maximum value of the parameter is also independently listed as (such as >8 and 9, all the following ranges should be expected: 1 to 8, 1 to 9, 2 to 8, 2 to 9, 3 to 8, and 3 to 9. Examples In the following examples, one of two different methods of neutralizing the latex was used: (1) Ammonia · Water by weight A 1 to 1 mixture with concentrated aqueous ammonia was added to the latex until the pH reached 7.5. (η) NaOH - A 5% by weight aqueous sodium hydroxide solution was added to the latex until the pH reached 7.5. In the following examples, the abbreviation "CA" Means DequestTM 2016, an aqueous solution containing approximately 20.5% (1-hydroxyethylidene) diphosphonic acid, sodium salt, and 〇 2% disodium hydrogenphosphonate (available from Solutia, Inc.). In each example, one of three levels of CA was used: 〇, 180 ppm CA, or 365 ppm ca (by weight based on the dry weight of the polymer). In the following examples, the two contents were One of the ferric sulphates was added to the aqueous composition 93190.doc -22-1302915. The amount of iron was recorded as ppm by dry weight of the polymer. The amount of iron used is 〇 or 6 ppm. In the following examples, the yellowness of the coating was measured by a Minolta colorimeter CR-200 (here, colorimeter π) as follows. It was coated on a 50.8 μηη (2 mil) polythene sheet (MylarTM from DuPont Co.) and dried in a forced air oven at l〇5 ° C for 3 minutes. The coating was smooth, smooth and clean. No defect, thickness 38.i gmG.5 mil) Soil 25 μπι (〇1 mi1) ° A second polyester film was laminated to the coating using a rubber roller. The resulting laminate was cut into 8 pieces. They are stacked on top of each other to prepare a test sample. The Yxy color space of the colorimeter is corrected to a standard white background according to the specification of the company, and then the b value of the test sample is measured and recorded as, without aging, b. Then place the test sample in a forced air oven and remove it from the furnace at 15 〇aC in 15 knives. 'Cool to room temperature, and measure the b value again. This time is recorded as aging" b value. 16 pieces of un-aged and aged non-coated film are also used in the same way. The stack was tested as a control sample in a colorimeter. Example U Latex Polymer LP1 A latex polymer (LP1) was prepared in the following manner: 890 g of deionized water was poured into a dad and heated to 89 ° C. The next step was to the kettle. A mixture of 0.9 g sodium carbonate in 22 g of water, 4.0 g of sodium persulfate in 34 g of water, and 30 g of a 45% solids propionate latex polymer having a particle size of 1 〇〇 nanometer was added and 3 liters of water was rinsed. After 5 minutes of control, 475 g of water, 17.4 g of sodium dodecylbenzenesulfonate (23%), 1 gram of butyl acrylate, 980 g of methyl methacrylate, and 20 g of acrylic acid monomer emulsion The mixture was slowly added to the dad for three and a half hours with a co-feed containing 1 g of sodium persulfate water (9 () g) dissolved in 93198.doc -23-1302915, followed by a 33 g water rinse. During the addition of the feed, the temperature was maintained at 8 6 °C. 30 minutes after the completion of the feed, the kettle was cooled to 60 ° C, and 16.7 g of a 0.15% solution of iron (II) sulfate was added, followed by two additions, each time from 1.2 g of the third butyl in 5.6 g of water. Hydrogen peroxide, and 0.72 g of formaldehyde sodium hyposulfite in 13.3 g of water. After adding the second supplement, the dad is cooled to below 40 °C. Example 2-5: Aqueous composition An aqueous composition of the following examples was prepared using the latex polymer LP1. Example # Neutralization ppm CA ppm Fe 0 5 0 5 8 6 8 6 11 3 11 3 0 0 6 6
2 NaOH2 NaOH
3 NaOH3 NaOH
4 NaOH4 NaOH
5 NaOH 實例CA-CE :對比性含水組合物 使用了膠乳聚合物LP1製得下列實例之含水組合物。 對比性實例# 中和 ppmCA ppmFe i8s 、：Η H 水水水o o 氨氨氨NaNa 0 0 5 0 0 8 6 1i 0 0 0 0 6 實例及對比性含水組合物之黃度 如上所述量測上述含水組合物之黃度之b參數。結果如 下： 93l98.doc -24- 1302915 組合物 未經老化之b 老化之h 對照樣品(僅聚酯薄膜） 3.1 3.0 CA 3.6 10.4 CB 3.6 9.4 CC 3.6 9.8 CD 3.6 3.7 3 8 CE 3.7 2 3.4 3.6 3 3.5 3.6 4 3.4 3.6 5 3.3 3.5 作為添加氣水之結果的黃度 再次測試實例4之組合物。 同時，藉 由將適當量之氨水溶 液添加至含水組合物中將1 〇〇 ppm氨添加至實例4之組合物 中且接著如上所述形成及測試該塗層 。將添加氨之樣品b 值置測兩次，且於此記錄其平均值。結果如下： 添加之氨(ppm)未經老化之b 老化之b ^ ~~33 100 3.3 4.4 93198.doc •25-5 NaOH Example CA-CE: Comparative aqueous composition An aqueous composition of the following examples was prepared using the latex polymer LP1. Comparative Example # neutralizing ppmCA ppmFe i8s , :Η H water water oo ammonia ammonia NaNa 0 0 5 0 0 8 6 1i 0 0 0 0 6 Examples and comparison of the yellowness of the comparative aqueous composition were measured as described above The b parameter of the yellowness of the aqueous composition. The results are as follows: 93l98.doc -24- 1302915 Composition unaged b aging h Control sample (polyester film only) 3.1 3.0 CA 3.6 10.4 CB 3.6 9.4 CC 3.6 9.8 CD 3.6 3.7 3 8 CE 3.7 2 3.4 3.6 3 3.5 3.6 4 3.4 3.6 5 3.3 3.5 The composition of Example 4 was again tested for yellowness as a result of the addition of gas water. At the same time, 1 〇〇 ppm of ammonia was added to the composition of Example 4 by adding an appropriate amount of aqueous ammonia solution to the aqueous composition and then the coating was formed and tested as described above. The sample b value of the added ammonia was measured twice, and the average value thereof was recorded here. The results are as follows: Added ammonia (ppm) without aging b aging b ^ ~~33 100 3.3 4.4 93198.doc •25-